Detergent formulations

ABSTRACT

COMPOUNDS HAVING THE FORMULA   R1-C(-COO-M)(-R2)-O-C(-COO-M)2-O-C(-COO-M)(-R2)-R1   WHEREIN M IS AN ALKALI METAL OR AMMONIUM AND R1 AND R2 ARE HYDROGEN OR METHYL IN COMBINATION WITH SURFACTANTS PROVIDE EFFECTIVE DETERGENT FORMULATIONS.

United States Patent 3,704,320 DETERGENT FORMULATIONS Kent P. Lannert,Freehurg, Ill., assignor to Monsanto Company, St. Louis, Mo. No Drawing.Filed June 30, 1971, Ser. No. 158,602 Int. Cl. C11d 1/38, 1/12 U.S. Cl.252-546 6 Claims ABSTRACT OF THE DISCLOSURE Compounds having the formula000M COOM COOM RlO-( JRl I l; 000M R1 wherein M is an alkali metal orammonium and R and R are hydrogen or methyl in combination withsurfactants provide effective detergent formulations.

BACKGROUND OF THE INVENTION This invention relates to novel detergentformulations characterized by novel detergency builder ingredients.

Numerous materials are known which, by virtue of sequesteringcharacteristics and/or capability to enhance the cleansing ability ofdetergent formulations in combination with various surfactants areuseful in water treating applications, or as adjuvants, re-enforcers,supplements, augmentors, potentiators, and/or benefactors in detergentformulations wherein such materials are usually referred to asdetergency builders. It is noted that although many detergency buildersare also sequestrants, the determination of materials which areeffective detergency builders is a complex matter empirical in natureand not accurately predictable from known characteristics of thematerials.

Many materials of the foregoing type are characterized by highphosphorous content such as the alkali metal tripolyphosphates widelyemployed as detergency builders. It has recently been suggested by someresearchers that such compounds may contribute to the acceleration ofeutrophication processes. Accordingly, particularly in the detergentbuilder field, extensive efforts have been exerted to provide alternatefunctional compounds free of phosphorus.

SUMMARY OF THE INVENTION It is an object of this invention to providenovel detergent formulations characterized by new and effectivedetergency builders.

The novel formulations of this invention will be understood from thefollowing description of the preferred embodiments.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The detergent formulations ofthis invention utilize, as detergency builders, the salt forms of novelcompounds represented by the formula wherein R is hydrogen, methyl,ethyl, alkali metal or ammonium and R and R are hydrogen or methyl.

The compounds are readily prepared reacting the appropriate alkylbromomalonate C O 0 (methyl or ethyl) H-O--Br O 0 (methyl or ethyl)3,704,320 Patented Nov. 28, 1972 in an inert solvent such as1,2-dimethoxyethane.

This reaction yields the ester forms of the compounds which aresaponified by conventional techniques to yield the desired ammonium oralkali metal salts. The acid forms of the compounds of this inventionare obtained by acidifying the salts. The acids can be crystallized byconventional techniques to provide useful precursors for high puritysalts. It is noted that when R is hydrogen, the acid is relativelyunstable due to a tendency to undergo rapid decarboxylation.

In preferred embodiments of the invention, R is sodium and R and R areboth methyl or hydrogen. These embodiments are preferred by virtue ofavailability of raw materials for their manufacture and their excellentperformance as detergency builders.

The detergent formulations of this invention will contain from 1 to byweight, preferably from 5 to 50% by weight of the salt, preferablysodium salt forms of the compound described. Such compounds can beutilized as the sole detergency builder in the compositions of thisinvention or in combination with other known detergency builders such aswater soluble inorganic builder salts, for example, alkali metalcarbonates, borates, phosphates, polyphosphates, bicarbonates andsilicates or organic builders such as salts of phytic acid, sodiumcitrate, water soluble polymeric polycarboxylates as described in U.S.Pat. 3,308,067 and the like.

The detergent formulations of this invention Will additionally containat least 8% by weight of a surfactant. Any of the numerous well-knownanionic, nonionic, zwitterionic or ampholytic surfactants can beemployed.

Examples of suitable anionic surfactants include alkyl ethyl sulfonates,alkyl sulfates, acyl sarcosinates; acyl esters of isocyanates, acylN-methyl taurides, and alkyl aryl sulfonates. The foregoing materialsare used in the form of their water-soluble sodium, potassium, ammo--nium and alkyl ammonium salts. Specific examples include sodium laurylsulfate; sodium N-methyl lauryl tauride; sodium dodecyl benzenesulfonate; and triethanol amine undecanol benzene sulfonate.

Examples of suitable nonionic detergents include alk'yl phenol andalcohol alkoxylates including condensates of l-decanol or l-undecanolwith from 3 to 5 molecular proportions of ethylene oxide such asdescribed in U.S. patent application Ser. No. 707,480 filed Feb. 23,196-8 and now abandoned; condensates of monohydroxy or polyhydroxyalcohols such as oleyl alcohol or l-trideca- 1101 with from 9 to 15molecular proportions of ethylene oxides; alkyl internal vicinaldialkoxy or hydroxy al koxy compounds as described in U.S. patentapplication Ser. No. 852,898 filed Aug. 25, 1969' and now abandoned; andcondensates of alkylene oxides with organo amines, for example, ethylenediamine and amides such as N-octadecyl diethanol amide.

Examples of cationic surfactants include octadecyl ammonium chloride;straight chain fatty amines having 8 to 18 carbon atoms; and quaternaryammonium compounds such as octadecyl trimethyl ammonium chloride.

Suitable ampholitic surfactants include the amido alkene sulfonates suchas sodium C-pentadecyl, N-methyl amido ethyl sulfonate potassium C-octylN-naphthalene amido propyl sulfonate; ammonium C-decyl, N-cyclo propylamido butyl sulfonate, and aliphatic amine derivatives in which thealiphatic substituent contains an anionic water solubilizing substituentsuch as a carboxy, sulfo, phosphato, or phosphino group, for example,sodium-3- dodecyl amino propionate'and' sodium-3-dodecyl amino propanesulfonate.

Examples of zwitterionic surfactants include derivatives of quaternaryammonium phosphonium and sulfonium. compoundssuch as 3-('N,N-dimethyl-Nhexa-' decyl ammonio) propane-l-sulfonate and3-(-N,N-dimethyl-N-hexadecyl ammonio-Z-hydroxy propane-l-sulfonate).

It will be understood that the above examples of supplementarysurfactants are by no means comprehensive.

Numerous other surfactants are known-to those skilled in the art and areset forth in suchfamiliar references asSurface Active Agents by A. M.Schwarzand James W.

Perry. Itwill be further: understood-that the use of such:

surfactants will be inaccordance with conventional,wellunderstoodpractices of detergent formulation. For example; cationicand anionic detergents will not normally be employed in combination Idue to I recognized problems of precipitation of insoluble products.

In accordance with general practice, the ratioof the detergency buildingcomponents to the surfactant components will be in the range of from 1:2to about 1221 by weight.

In addition to' surfactant and"builder'components, the

detergent formulations of this invention may containfillers suchassodium= sulfate and minor amounts of bleaches,-dyes, opticalbrighteners, soil anti-redeposition agents, perfumes and similarconventionaldetergent formulation additives.

The invention is further illustrated by the following examples whereinall parts and percentages are by weight unless otherwise indicated.

Example I C. The salt is precipitated by addition of excess ethanol andisolated byifiltr-ation and drying. Acidification of the salt with H SO.yields the acid formof the product.

Example II The salt and acid produced according-to Example I are testedfor sequestration characteristics-and are found to effectively sequesterCa++ ions.

Example I II V Detergent formulations containing 12% linear alkylbenzenesulfonate having. an average alkyl chaintlength of about 12carbon'atoms; from 5 to 75% of the salt form of the product of ExampleI; 12% sodium silicate having an SiO to 'Na O ratio of .about 2:4; and aquantity" of sodium sulfate sufiicient to equal 100% are found, inconventional laundry operations, to clean soiled samples of cotton andpolyester cotton broadcloth substantially better than otherwiseidentical formulations containing no builder salt. These testsdemonstrate that this material is an effective detergency buildermaterial.

4 Example 'IV The tests of Example I-II above are repeated using adetergent formulation in which 'Neodole 45-'1l (a nonionic surfactantwhich is-an adduct of a modified oxo type C C alcohol with an average of11 moles of ethylene oxide is substituted for the alkylbenzenesulfonate. Comparable results are obtained.

Example V The tests of Example III are repeated with a detergent"formulation wherein sodium h'ydroxyalkyl (C -C alkyl chain length)N-methyl taurate, and ampholytic surfactant, is substituted'for thealkylbenzene sulfonate. Comparable results are obtained.

Example VI The tests of Example 111 are repeated with a detergentformulation wherein cocodimethylsulfopropylbetaine, a zwitterionicsurfactant is substituted for the alkylbenzene sulfonate. Comparableresults are obtained.

What is claimed is:

1. A detergent composition consisting essentially of l at least 8% byweight of a surfactant selected from the group consisting of anionic,nonionic, zwitterionic, .ampholytic and amphoteric surfactants and from1% to by weight of a'detergency builder compound having the formula COOM0.00M 000M R2 00M R2 wherein Mis selected from the groupconsisting ofalkau metals and ammonium and R andR are eachselected from thegroupconsisting of hydrogen and methyl substituents.

2. A composition according to-claim 1" wherein said detergency'builderconstitutes from 5% to 50% of the weight of the composition.

31 A composition according to claim 1' wherein the surfactant is alinear alkylbenzene sulfonate surfactant.

4: A composition accordingto claim 1- wherein M is sodium.

5. A composition according to claim 4 wherein R is hydrogen" and R5 is amethyl substituent.

6. A composition according toclaim 4'wherein R and R are hydrogen.

References Cited UNITED STATES PATENTS 2,264,103 11/ 1941 Tucker 210-232,466,419 4/1949 Hagemeyer 260'5 35 3,635,830 1/ 1972 Lamberti 252-546-OTHER REFERENCES Journal of American Chemical Society: 62:1154.Bischolf: Berichte, vol. 40, pp. 3134, 3150 (1907). Bischofi: Berichte,vol. 29, 1276 (1896).

LEON D. ROSDOL, Primary Examiner P. E. WILLIS, Assistant Examiner U.S.C1. X-.R.

252-527, 531, 539, 550, 558, DIG.-11; 260-553 P

